EP0548162A1 - Flame retardant conductive polymer composition device - Google Patents
Flame retardant conductive polymer composition deviceInfo
- Publication number
- EP0548162A1 EP0548162A1 EP91916186A EP91916186A EP0548162A1 EP 0548162 A1 EP0548162 A1 EP 0548162A1 EP 91916186 A EP91916186 A EP 91916186A EP 91916186 A EP91916186 A EP 91916186A EP 0548162 A1 EP0548162 A1 EP 0548162A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- composition
- heater
- arc
- conductive polymer
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 98
- 229920001940 conductive polymer Polymers 0.000 title claims abstract description 32
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 title claims abstract description 14
- 239000003063 flame retardant Substances 0.000 title claims abstract description 13
- 238000012360 testing method Methods 0.000 claims abstract description 20
- 229920000642 polymer Polymers 0.000 claims abstract description 16
- 239000011231 conductive filler Substances 0.000 claims abstract description 13
- 239000006229 carbon black Substances 0.000 claims abstract description 12
- ADCOVFLJGNWWNZ-UHFFFAOYSA-N antimony trioxide Inorganic materials O=[Sb]O[Sb]=O ADCOVFLJGNWWNZ-UHFFFAOYSA-N 0.000 claims description 19
- 239000000945 filler Substances 0.000 claims description 17
- YEAUATLBSVJFOY-UHFFFAOYSA-N tetraantimony hexaoxide Chemical compound O1[Sb](O2)O[Sb]3O[Sb]1O[Sb]2O3 YEAUATLBSVJFOY-UHFFFAOYSA-N 0.000 claims description 17
- WHHGLZMJPXIBIX-UHFFFAOYSA-N decabromodiphenyl ether Chemical group BrC1=C(Br)C(Br)=C(Br)C(Br)=C1OC1=C(Br)C(Br)=C(Br)C(Br)=C1Br WHHGLZMJPXIBIX-UHFFFAOYSA-N 0.000 claims description 16
- 239000000463 material Substances 0.000 claims description 9
- CGPRUXZTHGTMKW-UHFFFAOYSA-N ethene;ethyl prop-2-enoate Chemical compound C=C.CCOC(=O)C=C CGPRUXZTHGTMKW-UHFFFAOYSA-N 0.000 claims description 2
- 229910052809 inorganic oxide Inorganic materials 0.000 claims 2
- GHPGOEFPKIHBNM-UHFFFAOYSA-N antimony(3+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Sb+3].[Sb+3] GHPGOEFPKIHBNM-UHFFFAOYSA-N 0.000 abstract description 4
- 238000000034 method Methods 0.000 description 7
- 239000008188 pellet Substances 0.000 description 7
- 229910052751 metal Inorganic materials 0.000 description 6
- 239000002184 metal Substances 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
- 229920001577 copolymer Polymers 0.000 description 5
- 239000002245 particle Substances 0.000 description 5
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 4
- 239000005977 Ethylene Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 229920001179 medium density polyethylene Polymers 0.000 description 4
- 239000004701 medium-density polyethylene Substances 0.000 description 4
- 229910044991 metal oxide Inorganic materials 0.000 description 4
- 150000004706 metal oxides Chemical class 0.000 description 4
- 239000003963 antioxidant agent Substances 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000000977 initiatory effect Effects 0.000 description 3
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- 239000000654 additive Substances 0.000 description 2
- 150000001336 alkenes Chemical class 0.000 description 2
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- WMWLMWRWZQELOS-UHFFFAOYSA-N bismuth(iii) oxide Chemical compound O=[Bi]O[Bi]=O WMWLMWRWZQELOS-UHFFFAOYSA-N 0.000 description 2
- YOCUPQPZWBBYIX-UHFFFAOYSA-N copper nickel Chemical compound [Ni].[Cu] YOCUPQPZWBBYIX-UHFFFAOYSA-N 0.000 description 2
- 229920001971 elastomer Polymers 0.000 description 2
- HQQADJVZYDDRJT-UHFFFAOYSA-N ethene;prop-1-ene Chemical group C=C.CC=C HQQADJVZYDDRJT-UHFFFAOYSA-N 0.000 description 2
- 238000001125 extrusion Methods 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 description 2
- 229920000620 organic polymer Polymers 0.000 description 2
- -1 polysiloxanes Polymers 0.000 description 2
- 230000001902 propagating effect Effects 0.000 description 2
- 230000002459 sustained effect Effects 0.000 description 2
- 150000004684 trihydrates Chemical class 0.000 description 2
- BLDFSDCBQJUWFG-UHFFFAOYSA-N 2-(methylamino)-1,2-diphenylethanol Chemical compound C=1C=CC=CC=1C(NC)C(O)C1=CC=CC=C1 BLDFSDCBQJUWFG-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 229920002943 EPDM rubber Polymers 0.000 description 1
- 239000002033 PVDF binder Substances 0.000 description 1
- 239000004952 Polyamide Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 241000872198 Serjania polyphylla Species 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- 229910052787 antimony Inorganic materials 0.000 description 1
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 description 1
- 229910000410 antimony oxide Inorganic materials 0.000 description 1
- LJCFOYOSGPHIOO-UHFFFAOYSA-N antimony pentoxide Inorganic materials O=[Sb](=O)O[Sb](=O)=O LJCFOYOSGPHIOO-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000010382 chemical cross-linking Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- 238000004132 cross linking Methods 0.000 description 1
- 239000003431 cross linking reagent Substances 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 150000001993 dienes Chemical class 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 239000000806 elastomer Substances 0.000 description 1
- 238000010292 electrical insulation Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- QHZOMAXECYYXGP-UHFFFAOYSA-N ethene;prop-2-enoic acid Chemical compound C=C.OC(=O)C=C QHZOMAXECYYXGP-UHFFFAOYSA-N 0.000 description 1
- VXNZUUAINFGPBY-UHFFFAOYSA-N ethyl ethylene Natural products CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 229920002313 fluoropolymer Polymers 0.000 description 1
- 239000004811 fluoropolymer Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 238000009434 installation Methods 0.000 description 1
- YADSGOSSYOOKMP-UHFFFAOYSA-N lead dioxide Inorganic materials O=[Pb]=O YADSGOSSYOOKMP-UHFFFAOYSA-N 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000395 magnesium oxide Substances 0.000 description 1
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 1
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 238000010128 melt processing Methods 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
- VTRUBDSFZJNXHI-UHFFFAOYSA-N oxoantimony Chemical compound [Sb]=O VTRUBDSFZJNXHI-UHFFFAOYSA-N 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229920002647 polyamide Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 239000004417 polycarbonate Substances 0.000 description 1
- 229920000515 polycarbonate Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 229920002981 polyvinylidene fluoride Polymers 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 239000005060 rubber Substances 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- BFKJFAAPBSQJPD-UHFFFAOYSA-N tetrafluoroethene Chemical group FC(F)=C(F)F BFKJFAAPBSQJPD-UHFFFAOYSA-N 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01C—RESISTORS
- H01C7/00—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material
- H01C7/02—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient
- H01C7/027—Non-adjustable resistors formed as one or more layers or coatings; Non-adjustable resistors made from powdered conducting material or powdered semi-conducting material with or without insulating material having positive temperature coefficient consisting of conducting or semi-conducting material dispersed in a non-conductive organic material
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/016—Flame-proofing or flame-retarding additives
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/02—Elements
- C08K3/04—Carbon
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B1/00—Conductors or conductive bodies characterised by the conductive materials; Selection of materials as conductors
- H01B1/20—Conductive material dispersed in non-conductive organic material
- H01B1/24—Conductive material dispersed in non-conductive organic material the conductive material comprising carbon-silicon compounds, carbon or silicon
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
-
- H—ELECTRICITY
- H05—ELECTRIC TECHNIQUES NOT OTHERWISE PROVIDED FOR
- H05B—ELECTRIC HEATING; ELECTRIC LIGHT SOURCES NOT OTHERWISE PROVIDED FOR; CIRCUIT ARRANGEMENTS FOR ELECTRIC LIGHT SOURCES, IN GENERAL
- H05B3/00—Ohmic-resistance heating
- H05B3/10—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor
- H05B3/12—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material
- H05B3/14—Heating elements characterised by the composition or nature of the materials or by the arrangement of the conductor characterised by the composition or nature of the conductive material the material being non-metallic
- H05B3/146—Conductive polymers, e.g. polyethylene, thermoplastics
Definitions
- This invention relates to conductive polymer compositions and strip heaters comprising them, in particular self-regulating strip heaters which comprise a pair of elongate metal electrodes embedded in an elongate core of a conductive polymer composition which exhibits PTC behavior.
- a conductive polymer composition comprises a polymeric component and, dispersed or otherwise distributed therein, a particulate conductive filler.
- strip heaters comprise a resistive element composed of a conductive polymer having elongate
- the resistive element is surrounded by an insulating jacket to provide electrical insulation and environmental protection.
- these heaters can be wrapped around or attached to a substrate, e.g. a pipe or a tank, and provide a varying level of heat in response to changes in the thermal environment. Under normal operating conditions, this self-regulating feature serves to limit the maximum temperature which the heater achieves, thus providing safety and reliability.
- a substrate e.g. a pipe or a tank
- a conductive polymer composition comprises a mixture of a nonconductive filler and a flame retardant, it can be used to make a heater which can have a a reduced tendency to propagate arcs.
- this invention related to a melt-extrudable conductive polymer composition which comprises
- a flame retardant said composition being such that when it is made into a standard strip heater as defined below and the heater is tested in a standard arc propagation test as defined below, an arc will not propagate.
- this invention relates to a heater which comprises (1) a resistive element which is composed of a conductive polymer composition as defined in the first aspect, and
- this invention relates to a strip heater which, when tested in the standard arc propagation test, will not propagate an arc, and which comprises
- this invention relates to a circuit comprising a heater as defined in the second or third aspect of the invention and a power supply.
- Figure 1 is a cross-sectional view of a standard strip heater of the invention
- Figure 2 is a top view of a strip heater of the invention
- Figure 3 is a cross-sectional view of a strip heater along line 3-3 of Figure 2; and Figure 4 is a circuit diagram of a circuit of the invention.
- the conductive polymer composition used in this invention comprises an organic polymer (such term being used to include polysiloxanes), preferably a crystalline organic polymer, an amorphous thermoplastic polymer (such as polycarbonate or polystyrene), an elastomer (such as polybutadiene or
- ethylene/propylene/diene (EPDM) polymer ethylene/propylene/diene (EPDM) polymer
- Suitable crystalline polymers include polymers of one or more olefins, particularly polyethylene;
- melt-shapeable fluoropolymers such as polyvinylidene fluoride and copolymers of ethylene and tetrafluoroethylene and
- crystalline polymers are particularly preferred when it is desired that the composition exhibit PTC (positive temperature coefficient of resistance) behavior.
- PTC behavior is used in this specification to denote a composition or an
- the composition should have an R 30 value of at least 6, where R 14 is the ratio of the resistivities at the end and the beginning of a 14°C temperature range, R 100 is the ratio of the resistivities at the end and the beginning of a 100°C range, and R 30 is the ratio of the resistivities at the end and the
- Heaters comprising conductive polymer compositions are described in U.S. Patent Nos. 3,858,144 (Bedard et al), 3,861,029 (Smith-Johannsen et al), 4,017,715 (Whitney et al), 4,242,573 (Batliwalla), 4,246,468 (Horsma), 4,334,148 (Kampe), 4,334,351 (Sopory), 4,398,084 (Walty),
- PCT/US 90/05102 filed September 10, 1990 (WO 91/03822, published March 21, 1991), and PCT/US 91/03123, filed May 7, 1991.
- the composition also comprises a particulate conductive filler which is dispersed or otherwise distributed in the polymer.
- the particulate conductive filler may be, for example, carbon black, graphite, metal, metal oxide, particulate
- the particulate conductive filler is present in the composition in an amount suitable for achieving the resistivity needed for the desired application.
- a particularly preferred particulate conductive filler is carbon black.
- the carbon black normally comprises 5 to 50% by weight of the composition, preferably 10 to 40% by weight, particularly 15 to 30% by weight. Larger quantities of carbon black may be required for use in applications requiring lower resistivities, e.g. circuit protection devices.
- the particulate nonconductive filler comprises a material which is electrically insulating and preferably has a
- the nonconductive filler has a melting temperature of less than 1000°C.
- Suitable materials include metal oxides which are easily reduced, e.g. Sb 2 O 3 , Sb 2 O 5 , PbO 2 , MoO 3 , Bi 2 O 3 , and NaSbO 3 .
- easily reduced means that the material has a reduction potential of less than +0.5 volts, preferably less than +0.4 volts, particularly less than +0.375 volts.
- the filler is preferably in the form of particles which have a particle size of 0.01 to 50 ⁇ m, particularly 0.05 to 50 ⁇ m, especially 0.10 to 10 ⁇ m.
- the nonconductive filler may be a single material or it may comprise two or more materials, e.g. a blend of metal oxides or a blend of a metal oxide and another particulate filler.
- a particularly preferred nonconductive filler is Sb 2 O 3 .
- Compositions which are particularly effective are those which comprise both carbon black and Sb 2 O 3 and in which the quantity (y) / (x + y) is at least 0.01, preferably at least 0.02, particularly at least 0.05, especially at least 0.10, e.g. 0.20 to 0.50, where x is the percent by weight of the carbon black and y is the percent by weight of the Sb 2 O 3 , based on the weight of the total
- compositions in which the polymer comprises a mixture of medium density polyethylene and ethylene/ethyl aerylate the Sb 2 O 3 is present in an amount at least 5%
- the composition used in this invention also comprises a flame retardant which may be added to the composition in any suitable form, e.g. a particulate filler or a liquid.
- the flame retardant is preferably a halogenated material. Particularly preferred is decabromodiphenyloxide (also known as
- DBDPO decabromodiphenylether
- compositions which are particularly effective are those which comprise both DBDPO and Sb 2 O 3 , and in which the quantity
- (y) / (y + z) is at least 0.10, preferably at least 0.15,
- the conductive polymer composition may also comprise inert fillers, antioxidants, chemical crosslinking agents, radiation crosslinking enhancement additives (prorads), stabilizers, dispersing agents, or other components.
- Mixing is preferably effected by melt-processing, e.g. meIt-extrusion or processing in a Banbury or other internal mixer. Subsequent processing steps may include extrusion, molding, sintering, or another procedure in order to form and shape the composition.
- the composition may be crosslinked, e.g. by irradiation or chemical means.
- the conductive polymer composition may be used in any current-carrying electrical device, e.g. a circuit protection device, a sensor, or, most commonly, a heater.
- the heater may be in the form of either a strip or a laminar sheet in which the resistive element comprises the composition of the invention.
- Strip heaters may be of any cross-section, e.g. rectangular, elliptical, or dumbbell ("dogbone").
- Appropriate electrodes, suitable for connection to a source of electrical power, are selected depending on the shape of the electrical device.
- Electrodes may comprise elongate metal wires or braid, e.g. for attachment to or embedment in the conductive polymer, or they may comprise metal sheet, metal mesh, conductive (e.g. metal- or carbon-filled) paint, or other suitable materials.
- Strip heaters of the invention are commonly used in a strip heater circuit which comprises the strip heater and a power supply.
- the power supply can be any suitable source of power, including portable power supplies and mains power sources.
- the circuit may incorporate a fuse, for example a slow-blow fuse, e.g. a standard glass-encapsulated fuse such as that available from the Bussman Division of Cooper Industries under the name BussmanTM 312 and having a rating of 250 volts/10 amps.
- the fuse may be an independent component in the circuit or it may be in a fused plug assembly, i.e. an assembly in which the fuse is part of the plug which connects the strip heater to the power source, e.g. an outlet or a power supply. Examples of fused plugs of this type are found in U.S. Patent Nos. 5,002,501 (Tucker, issued March 26, 1991) and
- a “standard strip heater” is one in which a conductive polymer composition is melt-extruded around two 22 AWG stranded nickel/copper wires to produce a strip heater of flat, elliptical shape as shown in Figure 1.
- the standard heater has an electrode spacing of 0.10 inch (0.25 cm) from the center of one electrode to the center of the second electrode.
- the thickness of the standard heater at a point centered between the electrodes is 0.07 inch (0.18 cm).
- the standard heater is jacketed with a 0.030 inch (0.076 cm) thick layer of the flameretarded composition used for the jacket material in Example 1.
- an arc is defined to be "non- propagating" if, in a standard arc propagation test as described below, it extinguishes itself, i.e. puts itself out, in less than 20 seconds from the time of arc initiation, or if it propagates a distance of less than 0.25 inch (0.64 cm),
- the Sb 2 O 3 acts as a catalyst to oxidize the carbon black in the conductive polymer with the resulting evolution of CO 2 and the elimination of carbon tracking paths . Concurrently, the Sb 2 O 3 is reduced to antimony metal which is conductive and creates a low resistance path through the polymer. In addition, the DBDPO acts synergistically with the Sb 2 O 3 to extinguish any flame which may liberate more carbon and result in more carbon tracks.
- Figure 1 shows a cross-section of a standard strip heater 1.
- Electrodes 5,7 are embedded in the conductive polymer
- composition 3 which provides the resistive element.
- a polymeric jacket 9 surrounds the heater core.
- Figure 2 shows a top view of strip heater 1 which has been prepared for the arc
- a V-shaped notch 11 is cut through the polymeric jacket 9 and the conductive polymer composition 3 on one surface of the heater in order to expose electrodes 5 and 7.
- the cross-sectional view of the prepared heater along line 3-3 is shown in Figure 3. Electrodes 5,7 remain partially embedded in the conductive polymer 3.
- Figure 4 shows a circuit of the invention which is
- a strip heater 1 is connected electrically in series with a power supply 13, a contact relay 15, and a shunt resistor 17.
- a chart recorder 19 is connected across the shunt resistor 17 and is used to measure the voltage drop when the contact relay 15 is closed and voltage flows through the circuit.
- Example 1 Comparative Example
- composition A in Table I The ingredients listed as Composition A in Table I were preblended and then mixed in a co-rotating twin-screw extruder to form pellets.
- the pelletized composition was extruded through a 1.5 inch (3.8 cm) extruder around two 22 AWG stranded nickel-copper wires to produce a strip heater with a relatively flat elliptical cross-section.
- the heater had an electrode spacing of 0.106 inch (0.269 cm) from wire center to wire center, a thickness of 0.067 inch (0.170 cm) at a center point between the wires, and a total width of about 0.172 inch (0.437 cm).
- the heater was jacketed with a 0.030 inch (0.076 cm) layer of a composition containing 10% ethylene/vinyl acetate copolymer (EVA), 36.8% medium density polyethylene, 10.3%
- EVA ethylene/vinyl acetate copolymer
- a standard, jacketed strip heater with a length of 25 inches (64 cm) was prepared by stripping one inch (2.5 cm) of jacket and conductive polymer material from a first end to expose the two electrodes.
- a transverse v-shaped notch was cut half-way through the thickness of the heater 2 inches (5.1 cm) from the second end and the jacket and conductive polymer were removed from the top half of the heater in order to expose part of each of the two electrodes.
- the electrodes at the first end were connected in a circuit in series with a 120V/100A power supply, a contactor relay, and a 0.1 ohm/100 watt shunt
- a chart recorder was connected across the shunt resistor in order to measure the voltage drop. When the relay was closed, the sample was powered at a voltage of 120 volts. A sufficient quantity of 10 to 20% saline solution was applied to the exposed v-notch to initiate an arcing fault. The chart recorder was monitored until the arc was extinguished. The distance of arc fault propagation on the strip heater, as well as the number and intensity of current spikes present during the arcing fault were measured.
- Example 2 Following the procedure of Example 1, the ingredients listed for Composition B in Table I were mixed, extruded, and jacketed to give a strip heater with the same dimensions as Example 1. Results of testing for arc propagation are shown in Table II.
- Example 3 Pellets of Composition A prepared following the procedure of Example 1 were pre-blended with a mixture of 26.9% by weight Sb 2 O 3 and 73.1% by weight decabromodiphenyloxide (DBDPO) to give a blend with the same formulation as Composition C in Table I. The blend was mixed in a co-rotating twin-screw extruder to form pellets and was then extruded and jacketed to produce a heater with the same dimensions as that in Example 1. Results of testing are in Table II.
- DBDPO decabromodiphenyloxide
- Composition A Pellets of Composition A prepared following the procedure of Example 1 were preblended with Sb 2 O 3 to give blends with the formulations listed in Table I as Compositions E, F, and G, respectively. Heaters were prepared and tested as in Example 4.
- Example 2 Pellets of Composition A prepared following the procedure of Example 1 were preblended with alumina trihydrate to give the blend listed in Table I as Composition I. Heaters were prepared and tested as in Example 4.
- Example 10 The composition of Example 2 (Composition B) was extruded through a 1.5 inch (3.8 cm) extruder around two 22 AWG stranded nickel-copper wires to produce a strip heater with a "dogbone" cross-section.
- the heater had an electrode spacing of 0.108 inch (0.274 cm) from wire center to wire center, a "web" thickness of approximately 0.040 inch (0.102 cm) at a center point between the wires, and a total width of about 0.154 inch (0.391 cm).
- the heater was jacketed as in Example 1. The results of testing are shown in Table II.
- Example 4 Using the composition of Example 4 (Composition D), a heater was prepared having the same geometry as Example 10. The results of testing are shown in Table II.
- EEA is ethylene/ethyl acrylate copolymer.
- CB is carbon black with a particle size of approximately 28 nm.
- MDPE medium density polyethylene
- AO is an antioxidant which is an oligomer of 4,4-thio bis(3- methyl 1-6-t-butyl phenol) with an average degree of polymerisation of 3 to 4, as described in U.S. Patent No, 3,986,981.
- Sb 2 O 3 is antimony trioxide with a particle size of 1.0 to 1.8 ⁇ m.
- DBDPO is decabromodiphenyloxide (also known as decabromodiphenylether).
- ATH is alumina trihydrate (Al 2 O 3 .3H 2 O) with a particle size of 0.15 ⁇ m.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Polymers & Plastics (AREA)
- Medicinal Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Dispersion Chemistry (AREA)
- Electromagnetism (AREA)
- Ceramic Engineering (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Thermistors And Varistors (AREA)
- Resistance Heating (AREA)
- Non-Adjustable Resistors (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US57975790A | 1990-09-10 | 1990-09-10 | |
US579757 | 1990-09-10 | ||
PCT/US1991/006533 WO1992004718A1 (en) | 1990-09-10 | 1991-09-10 | Flame retardant conductive polymer composition device |
Publications (3)
Publication Number | Publication Date |
---|---|
EP0548162A1 true EP0548162A1 (en) | 1993-06-30 |
EP0548162A4 EP0548162A4 (en) | 1993-11-24 |
EP0548162B1 EP0548162B1 (en) | 2001-12-19 |
Family
ID=24318235
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP91916186A Expired - Lifetime EP0548162B1 (en) | 1990-09-10 | 1991-09-10 | Flame retardant conductive polymer composition device |
Country Status (6)
Country | Link |
---|---|
EP (1) | EP0548162B1 (en) |
JP (1) | JP3140054B2 (en) |
AT (1) | ATE211296T1 (en) |
CA (1) | CA2090229C (en) |
DE (1) | DE69132877T2 (en) |
WO (1) | WO1992004718A1 (en) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8728354B2 (en) | 2006-11-20 | 2014-05-20 | Sabic Innovative Plastics Ip B.V. | Electrically conducting compositions |
Families Citing this family (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU5109099A (en) | 1998-07-15 | 2000-02-07 | Thermon Manufacturing Company | Thermally-conductive, electrically non-conductive heat transfer material and articles made thereof |
ATE522911T1 (en) * | 1998-12-04 | 2011-09-15 | Inditherm Plc | CONDUCTIVE MATERIALS |
US6974935B2 (en) | 1998-12-04 | 2005-12-13 | Inditherm Plc | Electrical connection |
NO319061B1 (en) * | 2003-05-15 | 2005-06-13 | Nexans | Lead-free electrical cable with high specific weight |
CN102427616B (en) * | 2011-09-02 | 2013-07-10 | 西安盖沃热能科技有限公司 | Flame-retarded PTC high polymer self-limiting temperature electric heating film and preparation method thereof |
CN102408606B (en) * | 2011-09-02 | 2012-12-19 | 西安盖沃热能科技有限公司 | Flame-retardant PTC (positive temperature coefficient) polymer electroconductive material and preparation method thereof |
Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH407543A (en) * | 1961-12-01 | 1966-02-15 | Kalk Chemische Fabrik Gmbh | Process for the production of high molecular weight plastics with increased flame resistance |
JPS5996148A (en) * | 1982-11-26 | 1984-06-02 | Showa Denko Kk | Ethylene copolymer composition |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1560759A (en) * | 1977-02-21 | 1980-02-06 | Pepper A R | Flame-retardant additive for polymeric compositions |
US4689475A (en) * | 1985-10-15 | 1987-08-25 | Raychem Corporation | Electrical devices containing conductive polymers |
JPH0777161B2 (en) * | 1986-10-24 | 1995-08-16 | 日本メクトロン株式会社 | PTC composition, method for producing the same and PTC element |
US4822983A (en) * | 1986-12-05 | 1989-04-18 | Raychem Corporation | Electrical heaters |
-
1991
- 1991-09-10 JP JP03515183A patent/JP3140054B2/en not_active Expired - Fee Related
- 1991-09-10 AT AT91916186T patent/ATE211296T1/en not_active IP Right Cessation
- 1991-09-10 EP EP91916186A patent/EP0548162B1/en not_active Expired - Lifetime
- 1991-09-10 CA CA002090229A patent/CA2090229C/en not_active Expired - Lifetime
- 1991-09-10 WO PCT/US1991/006533 patent/WO1992004718A1/en active IP Right Grant
- 1991-09-10 DE DE69132877T patent/DE69132877T2/en not_active Expired - Lifetime
Patent Citations (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CH407543A (en) * | 1961-12-01 | 1966-02-15 | Kalk Chemische Fabrik Gmbh | Process for the production of high molecular weight plastics with increased flame resistance |
JPS5996148A (en) * | 1982-11-26 | 1984-06-02 | Showa Denko Kk | Ethylene copolymer composition |
Non-Patent Citations (2)
Title |
---|
PATENT ABSTRACTS OF JAPAN vol. 8, no. 212 (C-244)(1649) & JP-A-59 096 148 ( SHOWA DENKO KK ) * |
See also references of WO9204718A1 * |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US8728354B2 (en) | 2006-11-20 | 2014-05-20 | Sabic Innovative Plastics Ip B.V. | Electrically conducting compositions |
Also Published As
Publication number | Publication date |
---|---|
JP3140054B2 (en) | 2001-03-05 |
EP0548162A4 (en) | 1993-11-24 |
DE69132877D1 (en) | 2002-01-31 |
ATE211296T1 (en) | 2002-01-15 |
WO1992004718A1 (en) | 1992-03-19 |
CA2090229A1 (en) | 1992-03-11 |
EP0548162B1 (en) | 2001-12-19 |
DE69132877T2 (en) | 2002-09-26 |
CA2090229C (en) | 2001-10-23 |
JPH06500662A (en) | 1994-01-20 |
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